2:1 metal complexes of 2,2&#39;,4&#39;-trihydroxy-3,5-dinitroazobenzene bound to a diphenylamine through an azo bridge

ABSTRACT

NEW METALLIZED POLYAZO DYES WHICH ARE NOTABLE FOR THEIR IMPROVED POWDER OF EXHAUSTION ON LEATHERS OF LOW AFFINITY AND ARE USED FOR DYEING AND PRINTING VARIOUS TYPES OF LEATHER. IT IS DESIRABLE FOR THESE DYES TO CONTAIN AS BASIC STRUCTRAL UNIT A GROUP OF THE FORMULA   1-((-)O-),3-(HO-),6-((2-((-)O-),3,5-DI(O2N-)PHENYL)-N=N-),   ((PHENYL-NH-)PHENYL)-N=N-)BENZENE 1-((-)O-),3-   (HO-),6-((2-((-)O-),3,5-DI(O2N-)PHENYL)-N=N-)BENZENE   ME(+4)   IN WHICH THE AROMATIC RING B BEARS PREFERABLY AN   -SO3H-   AND AN -NO2- GROUP. THE MOLECULE MAY CONTAIN UP TO THREE ADDITIONAL ARYLAZO GROUPS BUT PREFERABLY NOT MORE THAN ONE.

United States Patent 3,787,387 2:1 METAL COMPLEXES 0F 2,2,4'-TRIHYDROXY-3,5-DINITROAZOBENZENE BOUND TO A DI- PHENYLAMINE THROUGH AN AZO BRIDGEHeinz Wicki, Allschwil, Basel-Land, Switzerland, assignor to SandozLtd., Basel, Switzerland No Drawing. Filed Aug. 3, 1970, Ser. No. 60,748Claims priority, application Switzerland, Aug. 7, 1969, 11,976/ 69 Int.Cl. C09b 45/26, 45/32; D06p 3/32 US. Cl. 260-145 A 12 Claims ABSTRACT OFTHE DISCLOSURE New metallized polyazo dyes which are notable for theirimproved power of exhaustion on leathers of low afiinity and are usedfor dyeing and printing various types of leather. It is desirable forthese dyes to contain as basic structural unit a group of the formulaNoa in which the aromatic ring B bears preferably an SO H- and an NOgroup. The molecule may contain up to three additional arylazo groupsbut preferably not more than one.

This invention is directed to new metallized polyazo dyes which arenotable for their improved power of exhaustion on leathers of lowaffinity and are used for dyeing and printing various types of leather.It is desirable for these dyes to contain as their basic structural unita group of the formula on 0,N ran-O l 1 I= No,

in which the aromatic ring B bears preferably an and an NO group.

3,787,387 Patented Jan. 22, 1974 The invention thus relates to newmetallized polyazo dyes, and mixtures of the said dyes, which are of theformula R stands for hydrogen, halogen, nitro, substituted orunsubstituted alkyl or alkoxy, COOH or -SO H,

R for hydrogen, halogen, nitro, substituted or unsubtituted alkyl oralkoxy, COOH or -SO H,

R for hydrogen, halogen, nitro, substituted or unsubtituted alkyl oralkoxy, COOH or SO H,

R for hydrogen, halogen, nitro, substituted or unsubtituted alkyl oralkoxy, -COOH or SO H,

R, for the radical NH B Q a or the radical of a freely selected diazocomponent, Me for a metal atom, and n for 0 to 3.

The new dyes can be produced by coupling in either order 1 mole of thediazo compound from an amine of the formula ENQ QF R:

and 0 to 3 moles of the diazo compound from an amine of the formula 0and treating the resulting azo compound in substance with a metal donorto give the compound of Formula I.

4 Good dyes of the Formula I are obtained by coupling 1 and of theformula mole of a compound of the formula N0, OH s 0332 OH N=N-ONHONO,

OzN N=N oaN -N=N a 0 2 0 o o 1I=N N03 --N=N NO: 0

. N03 (IX) where Fe represents an iron atom.

with 1 mole of the diazo component from an amine of Formula H and 0 to 3moles of the diazo compound from g gi good azo dyes are those of thefollowing an amine of Formula HI. It is preferable for n to represent R1zero or the figure 1. Iron, chromium and cobalt com- NH pounds are ofspecial interest for the production of these metallized dyes. Good dyesare obtained when a coupling NO, N=N R: component of Formula Vcontaining iron, chromium or cobalt is used. OH R Equally good azo dyesare of the formulae N0, 02N N=1 I on B1 NH N=N R nfae om N=N o o no =N-No, No, (x)

R HO OH 1 0 NH N m N= R:

sonar 3 0H R IN N=l$ 0 g 0 NO R1 No, (X!) -N=N No,

N02 (VII) OaN N=I;I and in particular of the formula 011 80 H 5 a R,N=N-ONE R ogN N: R, N: N 05 a 5 R, A N=N N- N0: R

NH H0 N=N A R,

(VH1) (x11 OH R2 NO N=I:I

I T=N N02 1 102 (XIII) R1 ozN N=IT-- N=NC NEP 2 II=N NO l l O a OzN N=No 0 R2 I R1 -NOg S 0 3H H O 1 I S 03H Any of the known coupling methodscan be used. For instance, the coupling reaction yielding the monoazodye of Formula IV can be carried out in aqueous alkaline medium at atemperature from l0 C. to room temperature, if necessary in the presenceof sodium chloride.

Similarly, the coupling of the monoazo dye of Formula IV with adiazotized aminodiphenylamine or another diazo component to form thefinal dye can be carried out in aqueous alkaline medium at temperaturesof l0 C. to room temperature.

Metallization is best carried out in aqueous medium, with the additionof an organic solvent if necessary, or in an organic solvent alone. Forthi step of the process an acid medium is best, although metallizationcan also be accomplished in neutral to alkaline medium.

The suitable chromium compounds include chromium trioxide, chromicfluoride, chromic sulphate, chromic formate, chromic acetate, chromicpotassium sulphate and chromic ammonium sulphate. The chromates, e.g.sodium and potassium chromate and bichromate, are also highly suitablefor metallization. Iron and cobalt formate, acetate, sulphate andchloride exemplify the suitable iron and cobalt compounds.

In each instance halogen" represents bromine or fluorine, or preferablychlorine. The substituted or unsubstituted alkyl and alkoxy radicals arepreferably lower molecular and have 1, 2, 3 or 4 carbon atoms. If theyare substituted they bear, in particular, halogen atoms bydroxy or cyanogroups; these radicals then stand for methyl, ethyl, propyl, iso-propyl,butyl, iso-butyl, methoxy, ethoxy, cyanoethyl, hydroxyethyl,chloromethyl, chloroethyl, etc. Examples of suitable diazo componentsare those of substituted or unsubstituted aminobenzenes,aminonaphthalenes, aminohydroxynaphthalenes, aminonaphthalenesulphonicacids, aminohydroxynaphthalenesulphonic acids, etc. These latterradicals, and also the rings A and/or B, may be substituted by halogen,nitro, cyano, hydroxyl, amino, alkyl, alkoxy, sulphonic acid (sulfo),carboxyl, sulphonic acid or carboxylic acid amide (sulfamoyl orcarbamoyl), alkylsulphonyl, arylsulphonyl, etc. Alternatively, they maybe substituted by azo compounds.

The compounds of Formula I may bear 1 to 6, or optimally 1 to 4,identical or different sulphonic acid or carboxylic acid groups.

The metallized polyazo dyes of this invention are used for dyeing andprinting leather. They are notable for good power of build-up fromneutral to weakly acid dyebaths and good level dyeing properties. Onleathers tanned with difierent tanning agents they give dyeings ofconsistent shade which have good fastness to light, water, washing,perspiration, ironing and formaldehyde. The dyeings on chrome suedeleather show good bufling fastness. On leathers with low afiinity fordyes, such as those with a chrome-vegetable or chrome-synthetic tannage,the dyes build up to give dyeings of full depth; they also show goodexhaustion power from a neutral medium on this type of leather.

In relation to the nearest comparable dyes of French Pat. 1,431,548 thedyes of Formula I are of higher solubility, notably in water, and showsuperior levelling properties on grain leather.

In the following examples the parts are by weight and the temperaturesin degrees centigrade.

EXAMPLE 1 199 parts of Z-amino-4,6-dinitropl1enol are diazotized andcoupled at pH 9 with 110 parts of 1,3-dihydroxybenzene using the normalmethods. The resulting compound of Formula IV is isolated, stirred intowater and coupled at pH 9 by the normal method with the diazo compoundprepared from 309 parts (1 mole) of 4-amin0-4'-nito-2-sulphodiphenylamine.

To 1 mole of the disazo dye formed, which has the formula O H S 0 3H N MNK OzN- O H H is added 1 mole of the monoazo compound of Formula IV. Themixture is metallized in aqueous solution with 300 parts of ironsulphate at pH 4 and 100. The ironcontaining dye is isolated with sodiumchloride and dried. It is a brown powder which dissolves in water with adark brown color. It gives fasf, deep dyeings of red-brown shade onleather, especially on material showing low aflinity for dyes, such aschrome leather retanned with vegetable and synthetic tanning agents.

7 EXAMPLE 2 Two moles of the compound of Formula IV, formed as inExample 1, and a solution of 1 mole of iron sulphate in 500 parts ofwater and mixed in water at pH 4. The mix- 8 EXAMPLE 4 One mole of thecompound of Formula IV, produced as in Example 1, is stirred into 500parts of water and coupled at pH 9 with the diazo compound obtained withture is reacted for 1 hour at 98-100. The metallized dye 264 t f 4 2 I hh 1 is isolated and suspended in 500 parts of Water. At pH 9 par 5 o p 01p any amine the diazo compound, prepared with 309 parts of 4-amino- A fmole of f Q Q of Formula r i zr lph diph l i is dropped into the formedas in Example 1 1s stirred into 500 parts of water pension. Oncompletion of the coupling reaction the dye and Coupled f P 9 Wlih the(31320 compound from 172 is isolated with sodium chloride and dried. Itis obtained parts of p as a dark brown powder which dissolves readily inwater The tWO dlSaZO y SOIHUOIIS are Combmed, the P and gives fastred-brown dyeings on leather. value is adjusted to 4 and 300 parts ofiron-(HD-chlo- EXAMPLE 3 ride added. The solution is then raised to90-100 and held for 1 hour at this temperature for metallization. Sub-0116 m01e 0f the Q P 9 Formula IV Produced as sequently, sodium chlorideis added to isolate the given m Example 1 1s stirred into 500 parts ofwater and metallized dye formed on drying, a dark red bmwn, coupled atPE 9 Wlth the diam P g if g water soluble powder which dyes leather indark red- 22 alf z 5 drammo '3; o brown shades is obtained. gg izgfigggfigg i g 592 2 f g g The table below shows the structuralcomposition of mixture is stirred for 1 hour. When this couplingreaction gi 2 can i z z i accordfagce fi is complete, the solution isadjusted to pH 4 and 150 parts I e proce Si g o ey are 0 mm of ironsulphate are added. Metallization is then carried i are Spec y t 6compound P Formula V m out for 1 hour at 100. Afterwards the metallizeddye is the amme Formula H m colflmn the isolated with sodium chlorideand dried. It isadark brown amme of Formula In column C and H1 3 finalpowder, well soluble in water, which produces fast, dark column by theShade of i116 dyelng on leather given y red-brown dyeings on leather.the iron, cobalt and chromium complexes of the dye.

TABLE Component D Ex; of formula No; (V) Amine of formula (II) Amine offormula (III) Fe Co Cr 5 Compound CH; S 0;]?! CH3 Dark red- Dark Dark01' ormula I brown. giolet glolet Nr-ONH-ONOz NHa-O-S 03H 6 do (30011 on...do Do.-

NHz-ONH-QNO:

7 "do NH O NO M .--d0-.-......-do Do;

Q OaH 8 do Sameasabove SOsH .--do ..do Do.-

NEGRO, o (in do N138 do....-...-.do D0:

10 rln fin NH: (:H =:..do....-::.. do.-...= Do:

scams 0:11 11 (in fin IzilO '.:.d0..-.-'r;..d0 D0;

Nth-8s 003 12..-::::=:-d0.-...= (3H3 dn an D NE:- N0:

TABLE-#Contlnued Component D Ex. of formula No. (V) Amine of formula(II) Amine of formula (III) Fe Co Cr 13-- Compound z Dark red- Dark Darkof formual NH S 0 11 brown. violet violet brown; brown.

14.. :;-;:-.do.-..-:'.: NO: do do Do;

15 ..do S 03H $0311 .do. Do.-

16 do-. 00011 S O H -.-do ....--..do-....- Do.-

NHrO-NH-Q-NO: NHz- Noll 17 do COOH $02K -do.--...-..do-....- Do.

NHP NE MP S OaH Dyeing Example A In a drum dyeing machine 100 parts offreshly tanned, neutralized chrome grain leather are dyed for minutes at65 from a liquor consisting of 250 parts of water and 1 part of the dyesynthesized as given in Example 1. After this time 2 parts of an anionicfat liquor based on sulphonated train oil are added and drumming iscontinued for 30 minutes. The leather is then removed, dried understandard conditions and finished. The red-brown dyeing obtained on theleather is extremely level.

Dyeing Example B 100 parts of calf suede are wet back in a drum dyeingmachine for 4 hours in a bath of 1000 parts of water and 2 parts ofammonia. The bath is dropped and a fresh bath set with 500 parts ofwater, 2 parts of ammonia and 10 parts of the dye described inExample 1. The suede is drum dyed in this bath for 1 hour 30 minutes at65. T0 exhaust the dyebath, 4 parts of 85% formic acid are slowly added,after which the leather is drummed further to complete fixation of thedyeing. On removal the suede is rinsed, dried and finished by the normalmethods, and the nap buffed. The suede is dyed in a red-brown shade ofnotably good levelness.

Dyeing Example C 100 parts of chrome-vegetable tanned lambskin are dyedin a drum dyeing machine for 45 minutes at 55 from a bath of 1000 partsof water, 1.5 parts of an anionic sperm oil emulsion and 10 parts of thedye produced as in Example 1. The dyeing is fixed by the gradualaddition in 30 minutes of 5 parts of 85% formic acid. After the normaldrying and finishing treatments a leather is obtained dyed in a levelred-brown shade.

Dyeing Example D A solution of 20 parts of the dye of Example 1 in 847parts of water, 150 parts of ethyl glycol and 3 parts of 85 formic acidis applied to the grain side of a buffed, combination tanned sideleather, either by spraying, flow coating or with a plush pad. Theleather is dried under mild conditions and finished. A level, red-brownleather dyeing is obtained which has good fastness properties.

Formulae of representative dyes of the foregoing examples are asfollows:

Example 1 S 01H No, N=NONHON0 -1 I=N No,

Example 2 -N=N NE N0 9/ O- 2 Example 9 SOaH No, N: ONHONO:

OSIN -N=I;I

1 I=N -N 0,

1 N=N No:

Example 1 1 cm N=I)I 6 s o a o i N=N- NO;

on HO H035 N=N No,

Example 14 N0. N0: N=NONHOSO7H OzN 0 Having thus disclosed, theinvention what I claim is: 1. A dye of the formula each of R, R R and Ris independently hydrogen, halo,

nitro, alkyl, monosubstituted alkyl, alkoxy, monosubstituted alkoxy,carboxy or sulfo, wherein the substituent of each monosubstituted alkyland monosubstituted alkoxy is independently halo, hydroxy or cyano, andMe is iron, cobalt or chromium,

wherein each halo is independently chloro, bromo or fiuoro, and eachalkyl, alkoxy, alkyl chain of monosubstituted alkyl and alkoxy chain ofmonosubstituted alkoxy independently has 1, 2, 3 or 4 carbon atoms. 2. Adye according to claim 1 having the formula 1 I=N NO:

3. A dye according to claim 2 having the formula NO $0311 R1 o,N N=:

---IET=N N0: HOQ

4. A dye according to claim 3 having the formula 8. A dye according toclaim 2 having the formula NO, NO:

| SOIH I 1iz=N No,

H HO

Ill 0: 5. A dye according to claim 4 having the formula A dye accordmgto \8 havmg the formula NO IIIO: a

80:11 0H aH OH R:

0,N N=N a 0 0 o 0 N=N NO NO N 02 10.Thd coditl' h'thfl 6. A dye accordmgto claim 2 havmg the formula 6 ye a c r Hg 0 0 am 1 avmg e ormu a No, N:@4111 No, NH 40 I NO: N= RI OH I I s OH R OzN N=I:I

0m --N=lI- 0/ o O E 0 -N=N NO:

HO N 02 NO: 11. The dye according to claim 1 having the formula 7. A dyeaccording to claim 6 having the formula 12. The dye according to claim 1having the formula References Cited UNITED STATES PATENTS Biedermann eta1. 260-145 R Dehnert 260-145 R Wicki 260-145 R Steiner et a1 260-145 RFLOYD DALE HIGEL, Primary Examiner UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTION Patent No. 3 I787 387 Dated January 22 I 1974Inventor(s) HEINZ WICKI It is certified that error appears in theaboveidentified patent and that said Letters Patent are hereby correctedas shown below:

Column 2, lines 32-39, that portion of the formula reading u u t R NHQ 1should read NH 2 3 v a R Column 5, lines 20-34, that portion offormulaKXIV) reading SO H n 3 II p I R NH should read 7 1 R Column -6,line 56, "-nito-" should read nitr Claim 1, that portiQn of the formulareading l I n v 1 I R R Claim 4, that portion of the formula reading RII2 NH@ should read RM PC3-1050 (w'sg) I USCOMM-DC 6O376-P69 ".5.GOVERNMENT PRINTING OFFICEI l". '-3-3!l,

UNlTED STATES PATENT OFFICE (IER'HFICATE OF CORRECTION January 22, 1974Patent No. 3 1 Dated InVentor(S) HEINZ WICKI It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Claim 9, that portion of the formula reading H so H 2 should read 5 Y g?Signed and sealed this 16th day of July 197A.

(SEAL) Attest:

McCOY M. GIBSON, JR,, 0. MARSHALL DANN Attesting Officer Commissioner ofPatents "OR PC4050 10-69 M l uscoMMmc scan-poo t U.. GOVIRN"ENT PRINTINGOFFICE 2 '9. 0"36533.

